Process of transforming light paraffin hydrocarbons into other products



July 24, 1928. 1 ,678,078

A. S. RAMAGE PROCESS OF TRANSFORMING LIGHT PARAFFIN HYDROCARBONS INTO OTHER PRODUCTS Filed June 19, 1925 4 Sww-x m; ZZ/M 1114/1 Q1, QM may [5711214 (Zwmu w' r a v UNITED STATES PATENT OFFICE.

ALEXANDER S. RAMAGE,

ING 00., OF DETROIT,

OF DETROIT,

MICHIGAN, ASSIGNOB TO BOSTADH ENGINEER- MICHIGAN,

A CORPORATION 01 NEW YORK.

PROCESS OF TRANBFOBMING LIGHT PARAFFIN HYDROGABDONB INTO OTHER PRODUCTS.

Application filed June 19,

The present invention relates to the trans formation of mixtures of as those found in nature drocarbons such gas and those produc ing head gasolene,

pane, butane and pentane,

In United States Patent No.

roducts.

light parafiin hyed by weathering casfor instance, ethane, prointo other useful 1,224,787 I have described a. process for the conversion of parafiin hydrocarbons into other hydrocarbons containing proportionately less hydrogen,

penes and aromatic ectmg the parailin by such as olefines, terhydrocarbons, by subrocarbons to restricted oxidation or dehydrogenation by contacting them with a reducible metallic oxid, such as ferric oxid, at a temperature of say 580 to 750 C.

I have now dehydrogenation of light parafiin h found that the drocarbons may be so regulated that the ehydrogen-ation does not go olefine stage, by limiting the temperature 0 the oxidizing or dehydrogenation reaction about, but not The first step in the mate materially beyond the to rially above, 550 C. process of my present invention therefore consists in passing a mixture of light parafiin hydrocarbons or a gas containing the same,

or the wild gas from gasolene, over and 1n ible metallic oxid such such as natural gas weathered casing head contact with a reducas ferric oxid at a temperature not materially above 550 C.

This step may described in the referred to, excepting temperature employed be carried out precisely as is Patent No. 1,224,787 above with respect to the which is regulated so that the temperature of the gases leaving the apparatus does not materially rise above The product of thisoperation is a gaseous mixture containing olefines such as ethylene, propylene, togetber with fixed position is about 25% of higher olefines products which so gases.

and 40% far as the present invenbutylene and amylene,

An average comof ethylene, 25 to 35% of other gaseous tion is concerned may be regarded as impurities.

This gaseous mixture,

even when passed through a condenser and cooled with an ice and salt mixture,

does not give any appreciable quantity of condensate; but as I have found by cooling the gas mixture and then contacting it with a body of a solvent oil such as a hydroc arbon oil of the type knownas wash oil, the olefinic hydrocarbons are absorbed and poly merized. This may be 1 No. 1,527,079, of a standing high compression,

1925. Serial 170. 85,802.

regarded as a continuation of my earlier invention, as disclosed in United States Patent process for the polymerization of ethylene y absorbing it in a solvent hydrocarbon oil. This operation of absorbing the olefines from the gaseous mixture produced by the dehydrogenating operation frees the olefines from fixed gases which are not absorbed in the wash oil.

The next step in my process is the recovery of the olefines which may be accomplished by distillation of the wash oil mixture. In the distilling operation the polymerized olefines contained in the wash oil mixture are depolymerized or split up (this depolymerization occurs at about 120 F), giving a gaseous product consisting essentially of olefines and having an average composition corresponding to the formula CJI This gas has a calorific value of from 1? 3000-3500 B. t. u. per cubic foot.

In accordance with my invention this eousmixture of olefines may be treate in two ways: a) to produce a liquid consisting essentia ly of polymerized olefines ad mirably suited, due to its ability of with for use as fuel in aeroplane and other high-compression internal combustion engineaor (b) to produce a mixture of alcohols suitable for use for solvent purposes.

The production of a mixture of the polymerized olefines is accomplished by cooling the gas mixture distilled from the wash oil mixture and contacting it as by bubbling it into a body of the liquefied product thereof. By so doing the olefines contained in the gas are absorbed and polymerized to liquid products. This process of course requires as a startin material a quantity of the polymerized an li uefied olefines. uch a body of liquid may e provided in starting the process, for instance, by bubbling the olefinic gases into an absorbent oil such as wash oil and continuing the operation until the proportion of wash oil in the resulting liquid is negligible. Once the process has been started, the absorbing liquid may be sufpplied from a previous 0 eration. The lique ed product obtained as above, which is practically a pure mixture of the polymerized olefines is, as stated, admirably suited for use as motor fuel.

For the production of a mixture of alescribed eohols suitable for use as a solvent the prousual wa preferably to a coke residue. cedure is analogous to that emtployed for the The disti ate is a light yellow, pleasantproduction of ethyl alcohol r In the following description of an illusture of alcohols having excellent solvent trative procedure reference is made to the ropertles, being for instance a good solvent accompanying drawings in which oneform or gun-cotton. If des1red, it may of course of apparatus suitable for the carrying out be fractionally distilled to separate the variof the procedure is diagrammatica ly lllllS- ous alcohols. A trated. 7 It is of course understood that my inven- Referring to the drawings, 1, 2, 3 and 4 tion is not limited to the specific procedures are towers of conventional design which and apparatus described in the foregoing ma be, for instance, about feet in height specification, as it is evident that other pros and 4 feet in diameter and filled with a cedures and'other apparatus may be em- 7:; suitable acid-prooffilling material such as ployed. The (principal points of my invenfire-clay rings or balls. 5 is' an Inlet for t on are the ehydrogenatlon of 11 ht par- 1 the olefinic gases and 6 is an outlet for unaifin hydrocarbons under controll' condi-.

; contact with acid which has in the previous genation in wash 0 absorbed gases; 7 is a supply of fuming tions to produce a mixture of olefines, the sulfuric acid and 8 is .a receiver for the recovery of the olefines b absorbing them liquid or solution produced b the absorpin a solvent hquid, the pr notion of a liquid tion. -The towers are provide with pumps product by condensing the olefines in a liquid and conduits, as are usual for conveying product thereof and the conversion of the the gases from the top of the last tower of mixture of olefines into a mixture of 8.100- V the series numbered 4 into the bottom of hols. With the foregoing disclosure as a tower 3 and from the top-of tower 3 into guide, various methods of accomplishing the bottom of tower 2 and so on as indithese main points of my invention will be cated, and for conveying the acid to the, apparent to one skilled in this-art. distributor at the top of tower 1 andfrom It is possible, and may under certain cirom ethylene. smelling oil consisting essentially of a mix- 05 I the bottom of tower 1 to the top of tower cumstances be desirable, to eliminate the and so on as indicated. step of absorbing the olefines from the gas In the tower 4 the gases first come into mixture produced the limited dehydro- V towers absorbed a quantity of the olefines directly from the dehydrogenating operaand therefore is partially exhausted with tion the operations for the production of on respect to its absorbing capacity. In this a liquid product suitable for use as motor tower the higher and more easily absorbed fuel or for the production of alcohols. That olefines are absorbed. As the gases approach is, the gases may be cooled and absorbed dithe tower 1 the more readily absorbed olerectly in their own condensate or the gases es are removed until in t most diflicultly absorbed olefine, ethylene, sulfuric acid absorption.

comes in contact with fresh fuming sulfuric I cla1m:

. acid and is absorbed thereby and the un- 1. Process which comprises contacting a absorbed gases are discharged. As stated, mixture'of light para hydrocarbons subfuming sulfuric'acid is used for the absorpstantially unmixed with reactive oxygen 106 tion. I am aware that I might use instead with a reducible metal oxid'at a react of fuming sulfuric acid hot sulfuric acid temperature not substantially in excess of of 1.84 gravity, but I prefer to use fuming 550 C. f v 7,

acid and to operate at normal temperatures. 2. Process which comprises contactin a e tower 1 the may be passed directly after cooling to the loo The liquid product delivered from the mixture of hydrocarbons similar m by ro- 110 I tower 4 into the receiver 8 is diluted or carbon content to natural gas substantially mixed with an equal volume of water and unmixed with reactive oxygen with ferric the mixture heated in a lead-lined tank, oxid at a reactin temperature up to but not whereupon it separates into an upper layer exceeding 550 of a tar-like material and a lower layer 3. Process for the conversion of light 116 of diluted. sulfuric acid. The sulfuric acid parafiin hydrocarbons not heavier than may be disposed of in'any suitable way, for pentane into the correspond' olefines with-' instance it'may be concentrated and re-used out further substantial d 1ydrogenation in the absorbing operation. The tar-like which comprises contacting said paraflin mass is then treated with an aqueous soluhydrocarbons substantially unmixed with retion of caustic soda in quantity suflicient to active oxygen with ferric oxid at a temperproduce a practlcally neutral-reaction mixature of about 550 C. f ture. This operation gives a thick, brown, In testimony whereof,I afiix my signature. oily liquld which is then distilled in the ALEXANDER S. RAMAGE. 

